A thermodynamic distance criterion of optimality for the calculation of free energy changes from computer simulations

Schön, J. C.
December 1996
Journal of Chemical Physics;12/8/1996, Vol. 105 Issue 22, p10072
Academic Journal
The calculation of the external work expended during the switching between two systems yields bounds on their free energy difference. The quality of these bounds depends on the choice of path along which the work is calculated. In this paper, it is shown that for sufficiently fast relaxations the optimal path will be characterized by a minimal thermodynamic length, and that it should be parametrized such that it is traversed with constant thermodynamic speed. As an example, the optimal switching of a magnetic field containing a paramagnet is considered. Finally, the effects of finite relaxation times are discussed. © 1996 American Institute of Physics.


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